Shrinkproofing wool with compositions containing a polyester



United rates Patent 2,992,944 SHRINKPROOFING WOOL WITH COMPOSITIONS CONTAINING A POLYESTER Charles H. Binkley, Berkeley, Calif., assiguor to the United States of America as represented by the Secretary of Agriculture 9 No Drawing. Filed Nov. 13, 1959, Ser. No. 852,916

4 Claims. (Cl. 117-141) (Granted under Title 35, US. Code (1952), see. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to the treatment of textiles in order to improve their dimensional stability. The objects of the invention include the provision of novel processes for accomplishing such an end as well as the novel products so produced. By applying the teachings of the present invention, one is enabled to produce modified textiles which are dimensionally stabilized yet which retain unimpaired their intrinsic properties which make them useful for textile purposes. Thus, wool treated in accordance with the invention can be washed in aqueous media since it is highly resistant to shrinking and felting. However the treated wool is still useful for usual textile applications since the hand, resiliency, porosity, tensile strength, and other valuable properties of the textile are retained. A particular advantage of the treatment in accordance with the invention is that the improvement is essentially permanent; the treated textiles can be laundered or dry-cleaned repeatedly without losing their dimensional stability. A further advantage of the invention is that a relatively minor proportion of active agents deposited on the textile impart a very drastic improvement in dimensional stability. For example, wool treated in accordance with the invention with less than 10% of active material (polyepoxide, polyamide and polyester) displays virtually no shrinkage on repeated washing in aqueous media. The attainment of such a disproportionate improvement of the properties of the textile is indeed a result not to be expected by prior knowledge in this field. A further advantage of the process of the invention is that textiles treated in accordance with the invention can be dyed by ordinary dyeing procedures. For example wool treated by the procedures herein set forth may be dyed in conventional manner with the usual types of acid, chrome, premetalized, and milling dyes.

The process in accordance with the invention is to be distinguished from procedures wherein resinous materials are applied on textiles as continuous films. In such procedures the hand of the textile is completely altered so that the treated textile has more of the qualities of a plastic film than of a textile. Such products are totally unsuitable for conventional textile applications. In the process of the invention the polyepoxide, polyamide and polyester are applied in relatively small amounts and during the curing process react in situ on the textile fibers forming a resin coating on individual fibers rather than a exhibit poor dimensional stability. For example, washing causes severe shrinkages of woolen textiles. This 2,992,944 Patented July 18, 1961 technical disadvantage seriously restricts the applications of wool in the textile industry and much research has been understaken in order to modify the natural fiber to improve its strinkage properties. In recent years, the emphasis has been on impregnating the textile with various resins to give it improved dimensional stability. In particular, it has been demonstrated that wool may be rendered essentially shrinkproof by impregnating it with a composition containing (1) a polyepoxide, typically 2,2-bis(2,3-epoxy-propoxyphenyl)prcpane and (2) apolyamide, typically that derived from diethylene triamine and heat-dimerized unsaturated fat acids. The impregnated wool is then heated to efiect a cure, that is, to cause the polyepoxide and polyamide to react forming an insoluble resin coating on the fibers.

It has now been found that improved results are obtained when the process outlined above is modified by incorporating a special polyester with the polyepoxide and polyamide. Thus in accordance with the invention, woolen textiles are made essentially shrinkproof by impregnating them with a composition containing a polyepoxide, a polyamide, the special polyester and then curing the impregnated textile by application of heat. By applying the process of the invention, the following advantages are gained over and above those inherent in the known polyepoxide-polyamide treatment:

A primary advantage is that the treated fabric is more flexible and softer, that is, the treated fabric retains the hand of the original textile. For example, wool fabric having an original fiexural rigidity of -150 mg.-cm. when treated in accordance with the invention has a fiexural rigidity of -200 mg.-cm. whereas the same cloth treated by the known polyepoxide-polyamide process gives a flexural rigidity of 600 mg.-cm. or higher.

Another item is that the treated fabric shows a better hangout, or wrinkle recovery.

The treated fabric displays a better retention of the original color of the fabric.

Emulsions of the impregnating compounds are particularly easy to form because the polyester component promotes emulsifioation of the compounds in an aqueous system. Moreover the emulsions are stable and may be kept for long periods without gelling or loss of shrinkproofing effectiveness.

It is to be especially emphasized that the above advantages are gained without sacrifice of other factors. In particular there is no reduction in the degree of shrinkproofing effected. Further, addition of the polyester does not alter the excellent adhesiveness of the resin coating so that the shrinkproofing effect retains its permanence on repeated washing.

The special polyester employed in accordance with the invention is a glycerol-adipic acid polyester having an acid number from 50 to 180, preferably 100 to 150. The term acid number as used herein is defined as the number of rnillimols of free carboxyl per 100 grams of polyester. The significance of the acid number is that if this value is substantially lower than 50 the treated fabric is not significantly softer than that treated with the polyepoxide-polyamide composition without the polyester. On the other hand, polyesters with acid numbers over 180 cause reduction in the shrinkproofing effect.

The polyester is made by reacting glycerol and adipic acid under conventional esterification conditions, the reaction being continued until a polyester of the desired acid number is formed. Typically, glycerol and adipic acid-4n the proportion of about 4 moles of the former to 3 moles of the latter-are reacted at a temperature about from to 200 C. until a polyester of the desired acid number is formed. The reacting mixture is then cooled to stop further reaction. The polyesters are viscous, honey-like liquids. As in similar esterification,

the reaction is conducted under vacuum to draw off water of esterification and so drive the reaction in the desired direction. The time to stop the reaction may be ascertained in the customary manner by weighing the evolved water of esterification or by removing samples of the reaction mixture at intervals and determining the acid number of the product. This determination may be done by titration with 0.1 N sodium hydroxide using phenolphthalein as the indicator. The preparation of polyesters suitable for use in the process of the invention is illustrated in Example I to IV, below.

As noted briefly above, a step in the process of the invention involves impregnating the textile with the polyepoxide, polyamide, and polyester. To achieve uniform deposition of these agents on the textile it is preferred that they be applied to the textile in the form of a dispersion in a volatile, inert liquid carrier. The expression dispersion is used herein in a generic sense as including true solutions, colloidal solutions, suspensions, emulsions, etc. The application or impregnation is performed in any of the usual ways. For example, the dispersion is applied by spraying, brushing, dipping, etc. To assist in wetting the textile with the dispersion, the textile may be run through padding rolls or the like. Excess dispersion may be removed by passing the textile through wringer rolls. The proportion of active material in the dispersion and the amount of dispersion applied are usually so selected that there is deposited on the textile about 0.5 to 10% of its weight of the active material (polyepoxide, polyamide, and polyester). In general, the greater proportion of these materials deposited on the fiber, the greater the shrinkage protection afforded.

In accordance with a preferred embodiment of the invention, the polyepoxide, polyamide and polyester are deposited on the textile by impregnating it with an aqueous emulsion containing the three components. Such emulsions can be prepared by any of the known emulsification techniques. A preferred method of forming the emulsion involves dissolving each of the agents in a separate quantity of a volatile inert solvent, mixing the solutions and then incorporating this composite solution with a large quantity of water. In this way contact of the water will precipitate the agents in minute particles which are relatively easy to emulsify. The solvents used in forming the solutions may be such compounds as acetone, methyl-ethyl ketone, diethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethanol, propanol, isopropyl alcohol, butyl alcohols, etc. Ordinarily it is unnecessary to employ any emulsifying agent in forming the emulsion as the polyester component facilitates the emulsifioation. Indeed, this is one of the advantages in using the polyester.

Although it is preferred to use emulsions, the polyepoxide, polyamide and polyester may be applied to the textile in other dispersed forms. Thus for example the agents may be dissolved in a volatile inert organic solvent such as those exemplified above and the resulting solution applied to the textile.

It is evident from the above that the dispersion applied to the fabric contains the polyepoxide, polyamide, and polyester in solution, emulsion, or suspension depending on the liquid medium chosen. The total concentration of the three agents in the dispersion is not critical and may be varied as desired to deposit on the fabric the desired total percentage of the three agents. Generally the dispersions will contain a total percentage of 1 to 10% of polyepoxide, polyamide, and polyester. The relative proportions of these agents in the dispersion may be varied. For example, considering the proportion of polyepoxide fixed at one part, the proportion of polyester may be varied from 0.5 to 2 parts, preferably 1 to 1.25 parts thereof; the proportion of polyamide may be varied from 0.1 to 5 parts, preferably 0.5 to 1.5 parts thereof.

After the textile has been impregnated with the poly epoxide, polyamide, and polyester, it is subjected to a curing treatment. This simply involves heating the textile to promote reactions between the three agents whereby there is formed an insoluble resinous reaction product on the fibers. The resinous material dimensionally stabilizes the textile permanently since it is essentially insoluble in water, aqueous washing media, dry cleaning solvents, etc. The curing treatment is generally conducted at temperatures in the range 50 to 200 C., more preferably -200 C. The time for cure will vary depending on such factors as the reactivity of the polyepoxide, polyamide and polyester selected and particularly on the temperature at which the cure is carried out. For example, the cure may require more than 30 minutes at 100 0., about 10 to 30 minutes at C., about 3 to 15 minutes at C. and 5 minutes or less at C. A preferred type of treatment involves first drying the treated textile in a current of air at about 20 to 50 C. to remove liquid carrier (water, alcohol, or other solvent) then curing in an oven at 125-l50 C. for 10 to 20 minutes. Although the curing is generally done by heating in an oven, it can be carried out by applying hot water or steam to the treated fabric. Also the fabric may be cured by pressing with a steam or dry iron or by subjection to radiant heat.

In one modification of the invention the mixture of polyepoxide, polyamide, and polyester is subjected to a pro-polymerization prior to being formed into an emulsion. This procedure is desirable to produce particularly stable emulsions which may be kept for many months with no coagulation, sedimentation, or loss of shrinkproofing power. In carrying out this step, the three compounds are dissolved in an inert volatile solvent, such as acetone, methyl-ethyl ketone, diethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethanol, propanol, isopropyl alcohol, any of the butyl alcohols, etc. The solution is then held at a temperature which may be as low as room temperature (25 C.) or for faster reaction at elevated temperatures up to 100 C. or at least up to the boiling point of the solvent used. The time required will depend on such factors as the concentration of the components and particularly on the temperature. For example, storing at room temperature requires about 12-16 hours whereas heating at 175 F. requires about 2 to 4 hours. In any particular case it is preferred to gauge the degree of prepolymerization by pouring small portions of the solution into water at intervals and noting the appearance of the emulsion found. That is, the reaction is continued until an opalescent to clear emulsion is formed when the test is made. When this point is reached the heating is discontinued. In any event the solution should not be heated beyond the point of forming an opalescent to clear emulsion or coagulation will occur.

To ensure uniform deposition of the polyester, polyepoxide, and polyamide on the textile, it is preferred that the textile prior to application of these agents be in a clean state and free from spinning oils, lubricants, and other extraneous materials. To this end the textile before application of the polyester, polyepoxide and polyamide-may be scoured with conventional aqueous Washing media containing soap or synthetic detergents. In the alternative, the textile may be extracted with fatsolvents such as benzene, Stoddard solvent, naphtha, carbon tetra-chloride, ethanol, or the like. It is also preferred that the textile material be in a neutrad to slightly alkaline state (pH about 7 to 9) prior to application of the polyester, polyepoxide, and polyamide since acid conditions (as may be encountered with wool dyed in acid baths) will hinder the desired reaction between epoxy groups of the polyepoxide and the amino groups of .the polyamide. Generally, where the textile is washed in conventional soap or detergent-containing media it will be at a proper pH for the treatment. If the textile is in an acid condition it may be properly conditioned by soaking in a dilute solution (about 0.1 to 5%) of a mild alkaline agent such as sodium carbonate, sodium bicarbonate, borax, trisodium phosphate, tetrasodium pyrophosphate, sodium metaphosphate, ammonia, sodium acetate, soap, or the like. After such soaking the textile may be rinsed with water and dried.

The polyepoxides used in accordance with the invention are organic compounds having at least two epoxy groups per molecule and may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted with non-interfering substituents such as hydroxyl groups, ether radicals, and the like. Polyepoxides containing ether groups, generally designated as polyepoxide polyethers, may be prepared as well known in the art by reacting a polyol with a halogen-containing epoxide employing at least 2 moles of the halogen-containing epoxide per mole of polyol. Thus, for example,

' epichlorhydrin may be reacted with a polyhydric phenol in an alkaline medium. In another technique the halogencontaining epoxide is reacted with a polyhydric alcohol in the presence of an acid-acting catalyst such as hydrofluoric acid or boron trifiuoride and the product is then reacted with an alkaline compound to effect a dehydrohalogenation. A preferred example of the halogen-containing epoxide is epichlorhydrin; others are epibromhydrin, epiodohydrin, 3-chloro-1,2-epoxybutane, 3-bromo-1, 'Z-epoxyhexane, and S-chloro-1,2-epoxyoctane. Examples of polyols which may be reacted with the halogen-conraining epoxide are glycerol, diglycerol, propylene glycol, ethylene glycol, diethylene glycol, butylene glycol, hexanetriol, sorbitol, mannitol, pentanetriol, pentaerythritol, dipentaerythritol, polyglycerol, dulcitol, inositol, carbohydrates, methyltrimethylol propane, 2,6-octanediol, tetrahydroxycyclohexane, 2-ethyl hexane-triol-l,2,6, glycerol methyl ether, glycerol allyl ether, polyvinyl alcohol,

polyallyl alcohol, resorcinol, catechol, hydroquinone, 4,

glycol diglycidyl ether; diethylene glycol diglycidyl ether;

resorcinol diglycidyl ether; 1,2,3,4-tetrakis(2-hydroxy-3, 4-epoxybutoxy) butane; 2,2-bis 2,3-epoxypropoxyphenyl) propane; glycerol triglycid'yl ether; mannitol tetraglycidyl ether; pentaerythritol tetraglycidyl ether; sorbitol tetraglycidyl ether; glycerol di-glycidyl ether; etc. It is evident that the polyepoxide polyethers may or may not contain hydroxy groups, depending primarily on the proportions of halogen-containing epoxide and polyol employed. Pol-yepoxide polyethers containing polyhydroxy groups may also be prepared by reacting, in known manner, a polyhydric alcohol or polyhydric phenol with a polyepoxide in an alkaline medium. Illustrative examples are the reaction product of glycerol anddiglycidyl ether, the reaction product of sorbitol and bis(2,3-epoxy-2-methylpropyl)ether, the reaction product of pentaerythritol and 1,2,3,5-diepoxy pentane, the reaction product of 2,2-bis (parahydroxyphenyl)propane and bis(2,3 epoxy 2 methylpropyl)ether, the reaction product of resorcinol and diglycidyl ether, the reaction product of catechol and CH2CH-CH2PO The phenol moiety may be completely etherified or may contain residual hydroxy groups. Particularly preferred among the glycidyl polyethers are those derived from 2,2-

bis (parahydroxyphenyl)propane. These compounds have the structure wherein It varies between zero and about 10, corresponding to a molecular weight about from 350 to 8,000. Of this class of polyepoxides I prefer to employ those compounds wherein n has a low value, i.e., less than 5, most preferably where n is zero. These compounds are preferred because they yield a maximum degree of shrinkproofing with a minor amount thereof deposited on the fabric. However, these compounds when employed only in conjunction with polyamides, that is without the special polyester, produce hard and still? treated fabrics. It is a special feature of the invention that these glycidyl ethers of 2,2-bis(parahydroxyphenyl)propane may be utilized advantageously to yield maximum shrinkproofing without stiffening of the treated fabric.

The polyamides used in accordance with the invention are those derived from polyamines and polybasic acids. Methods of preparing these polyamides by condensation of polyamines and polycarboxylic acids are well known in the art and need not be described here. One may prepare polyamides containing free amino groups or free carboxylic acid groups or both free amino and free carboxylic acid groups. Generally it is preferred to employ polyamides which contain free amino groups since the active hydrogens on these groups are especially reactive with the epoxy groups of the polyepoxide to form insoluble polyepoxide-polyamide reaction products. The polyamides may be derived from such polyamines as ethylene diamine; diethylene triamine; triethylene tetramine; tetraethylene pentamine; 1,4-diamino-butane; 1,3- diaminobutane; hexamethylene diamine; 3-(N-isopropylamino)-propylamine; 3,3-imino-bispropylamine; and the like. Typical polycarboxylic acids which may be condensed with the polyamines to form polyamides are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, beta-methyl adipic acid, 1,2-cyclohexane dicarboxylic acid, malonic acid, polymerized fat acids, and the like. Depending on the amine and acid constituents and the conditions of condensation, the polyamides may have molecular weights varying about from 1,000 to 10,000 and melting points about from 20-200 C. Particularly preferred for the purpose of the invention are the polyamides derived from aliphatic polyamines and polymeric fat the polymerization of drying or semi-drying oils, or the free acids, or simple aliphatic alcohol esters of such acids.

aseaeee The polymeric fat acids may typically be derived from such oils as soybean, linseed, tung, perilla, oiticica, cottonseed, corn, tall, sunflower, safflower, and the like. As well known in the art, in the polymerization the unsaturated fat acids combine to produce a mixture of dibasic and higher polymeric acids. Usually the mixture contains a preponderant proportion of dimeric acids with lesser amounts of trimeric and higher polymeric acids, and some residual monomeric acid. Particularly preferred are the polyamides of low melting point (about 20-90" C.) which may be produced by heating together an aliphatic polyamine, such as diethylene triamine, triethylene tetramine, 1,4-diaminobutane, 1,3-diaminobutane, and the like with the polymerized fat acids. Typical among these is a polyamide derived from diethylene triamine and dimerized soybean fatty acids.

The process of the invention may be applied to allwool textiles or textiles containing wool blended with other fibers, for example: animal hair; mohair; silk; synthetic fibers made from proteins such as Zein, casein, peanut protein, soybean protein, keratins, etc.; cellulosic fibers such as cotton, linen, rayon, viscose, cellulose, acetate, jute, hemp, etc.; nylon; dynel; Orlon; Dacron; or other organic textile fibers. The expression wool-containing textile as used herein is intended to encompass all-wool textiles and blended textiles containing a significant proportion, that is, at least 25% by weight of wool. The process of the invention may be applied to wool-containing textile materials in the form of fibers, threads, yarns, slivers, woven or knitted fabrics, or even garments made of woven or knitted fabrics. The textiles may be white or dyed goods.

The invention is further demonstrated by the following examples which are given only by way of illustration but not limitation.

Example I.Preparation of polyester The ingredients listed below were introduced into a flask provided with a thermometer for measuring the temperature of the contents and equipped for operation at reduced pressure:

Adipic acid 876.6 grams (6 moles) Glycerol 736.8 grams (8 moles) The temperature in the flask was raised to 182 C., keeping the flask open, in 55 minutes. The pressure in the flask was then reduced to about 20 mm. Hg and heating was continued for 1 hr. and 10 minutes with the temperature varying from 155 to 185 C. At the end of this time the reaction mixture was cooled. The polyester had an acid number of 166.

Example Il.Prepardtin of polyester Adipic acid (6 moles) and glycerol (8 moles) were heated together in the equipment described in Example I until there was vigorous boiling. Boiling was continued until the temperature rose to 193 C. The pressure in the flask was then reduced to about 20 mm. Hg. Heating at the same rate was continued for 7 minutes then discontinued while the system was retained under vacuum for minutes more. The cooled product had an acid number of 150.

Example lII.Pl eparati0n of polyester Adipic acid and glycerol, in a molar ratio of 3 to 4, Were'placed in the vessel described in Example I and heated for 1 /4 hours at 185 C. while the flask was evacuated by connection to a conventional water aspirator. The polyester was a viscous liquid with an acid number of 105.

Example IV.Preparation of polyester A series of polyesters was prepared. In each case the charge was 6 moles of adipic acid and 8 moles of glycerol. The reaction mixtures were brought to the boil then held at reaction temperatures between 150 and 200 C. under vacuum for .varying periods of time. The products had the following properties.

Example V.--Preparation of padding emulsion The following solutions were made:

(a) Four grams of the polyester of Example III was dissolved in 4 ml. of 2-ethoxyethanol.

(12) Four grams of polyepoxide was dissolved in 4 ml. of methyl ethyl ketone. The polyepoxide was a commercial product (Epon 828), essentially 2,2,-bis(2,3- epoxy-propoxyphenyl)propane prepared by reacting epichlorhydrin with 2,2,-bis(parahydroxyphenyl)propane.

(c) Four grams of polyamide was dissolved in 4 ml. of methyl ethyl ketone. The polyamide was a .commercial product (Versamide 115), a condensation product of diethylene triamine and heat-dimerized unsaturated fat acids.

The three solutions were then mixed together and the composite solution was poured into 375 ml. of water, stirring with a paddle during addition of the solution.

The resulting pale-milky emulsion is useful for padding wool to be shrinkproofed.

Example VI.Preparati0n of padding emulsion The following solutions were made:

(a) Twenty-seven grams of the polyester of Example III was dissolved in 25.7 ml. of a solvent containing 2- ethoxyethanol, methyl ethyl ketone, and n-propanol in the respective volumetric proportions 19, 40.5, and 16.2.

(b) Twenty-seven grams of the polyepoxide described in Example V was dissolved in 25 ml. of the same solvent.

(c) Twenty-seven grams of the polyamide described in Example V was dissolved in 25 ml. of the same solvent.

The three solutions (a, b, and 0) were then mixed to gether and heated in a closed container to 175 F. (79.4 C.) and held at that temperature for minutes. The hot solution was poured into 500 ml. of water, while stirring with a paddle. The resulting milky to opalescent emulsion was then diluted to contain 4% solids.

Example V1l.-St0rage of emulsion The emulsion descriped in Example VI was further diluted with water to 3% total solids and stored at room temperature in a screw-cap jar. After 10 months storage the emulsion showed no coagulation, no sediment.

Example VIII.Shrinkp0ofing treatment A piece of wool flannel, non-finished griege goods, with a pH of approximately 7 was dry cleaned with Stoddard solvent and dried free of solvent. The cloth was dipped into the emulsion described in Example V and run through squeeze rolls giving a weight increase of The impregnated fabric was dried in air to about 30% moisture then heated in a hot air draft oven for 30 minutes at 250 F. (121 -C.). The treated fabric had a resin uptake of about 2.25%.

For comparison purposes, a piece of the same cloth was treated with the same emulsion but with the polyester omitted, that is, containing only the polyepoxide and polyamide. The impregnated cloth was heat-cured as before. i

The two treated cloth samples and a sample of the original untreated cloth were then subjected to a series of tests as described below.

Washing test-The samples were agitated in an accelerator at 1780 rpm. for 2 min. in a 0.5% solution of sodium oleate at 40 C. with a cloth to solution ratio of 1:35, the area of the cloth being measured before and after drying.

Flexural rigidity.-This property was measured in the warp direction by the cantilever method ASTM D-l388- 5ST. In this test a higher value indicates a stiffer fabric.

Wrinkle recovery.-The cloths were folded accordionfashion with the folds one inch apart and pressed with a 200 gram weight for 1 minute then hung by one end for four days. While so hanging a light was directed obliquely along the surface of the cloth and the light reflected normal to the surface was impinged on a moving photoelectric cell. Measurements were then made of the ratio of the amount of light reflected from the brightly illuminated surfaces to the amount of light reflected from the shadowed surfaces illuminated to a lesser extent. In this test a lower ratio indicates a flatter surface, that is, better wrinkle recovery whereas a high ratio indicates a more highly wrinkled surface.

The results obtained are tabulated below:

Pieces of bleached wool flannel having a pH of about 8.5 were immersed in the emulsion of Example VII (which had been stored for months). The cloth was then passed through squeeze rolls, dried in air and cured in an oven at 250 F. The treated cloth had a resin uptake of 4.4%.

Samples of the treated cloth and the untreated cloth were subjected to the washing test described in Example VIII. Area shrinkage of the treated cloth was 3% whereas that of the untreated cloth was 55%. It was also observed that the treated cloth was as soft as the original cloth and showed no decrease in hang-out or wrinkle recovery. Also the treated cloth showed no evidence of yellowing but was of the same color as the original cloth.

Having thus described the invention, what is claimed 1s:

1. The process of shrinkproofing a wool-containing textile Without significant impairment of its hand which comprises impregnating the textile with (A) a polyepoxide containing at least two epoxy groups per molecule, (B) a polyamide of an aliphatic polyamine and a polycarboxylic acid, said polyamide containing free groups selected from the class consisting of amine groups and carboxyl groups, and (C) a glycerol-adipic acid polyester having an acid number from 50 to 180, the total amount of polyepoxide, polyamide, and polyester deposited on the textile being about from 0.5 to 10% of the weight of the textile, the amount of polyester being about from 0.5 to 2 parts by weight for each part by weigh of polyepoxide, and curing the impregnated textile by heating it at an elevated temperature to cure and insolubilize the polyepoxide, polyamide and polyester on the textile fibers.

2. The process of shrinkproofing wool without significant impairment of its hand which comprises impregnating wool with (A) a glycidyl polyether of 2,2.-bis(parahydroxyphenyl)propane, (B) a polyamide of a lower aliphatic polyamine and a polymeric fat acid containing at least two carboxyl groups, said polyamide having free amine groups, and (C) a glycerol-adipic acid polyester having an acid number from 50 to 180, the total amount of polyepoxide, polyamide, and polyester deposited on the wool being about from 0.5 to 10% of the weight of the wool, the amount of polyester being about from 0.5 to 2 parts by weight for each part by weight of polyepoxide, and curing the impregnated wool by heating it i at an elevated temperature to cure and insolubilize the polyepoxide, polyamide and polyester on the wool fibers.

3. Shrinkproofed wool-containing textile material of substantially unimpaired hand comprising textile fibers carrying a heat-cured deposit of (A) a polyepoxide containing at least two epoxy groups per molecule, (B) a polyamide of an aliphatic polyamine and a polycarboxylic acid, said polyamide containing free groups selected from the class consisting of amine groups and carboxyl groups, and (C) a glycerol-adipic acid polyester having an acid number from 50 to 180, the total amount of said polyepoxide, polyamide, and polyester being about from 0.5 to 10% of the weight of the textile, the amount of polyester being about from 0.5 to 2 parts by weight for each part by weight of polyepoxide.

4. Shrinkproofed wool of substantially unimpaired hand comprising wool carrying a heat-cured deposit of (A) a glycidyl polyether of 2,2-bis(parahydroxyphenyl)- propane, (B) a polyamide of a lower aliphatic polyamine and a polymeric fat acid containing at least two carboxyl groups, said polyamide having free amine groups, and (C) a glycerol-adipic acid polyester having an acid number from 50 to 180, the total amount of said polyepoxide, polyamide, and polyester deposited on the wool being about from 0.5 to 10% of the weight of the wool, the amount of polyester being about from 0.5 to 2 parts by weight for each part by weight of polyepoxide. 

1. THE PROCESS OF SHRINKPROOFING A WOOL-CONTAINING TEXTILE WITHOUT SIGNIFICANT IMPAIRMENT OF ITS BAND WHICH COMPRISES IMPREGNATING THE TEXTILE WITH (A) A POLYEPOXIDE CONTAINING AT LEAST TWO EPOXY GROUPS PER MOLECULE, (B) A POLYAMIDE OF AN ALIPHATIC POLYAMINE AND A POLLYCARBOXYLIC ACID, SAID POLYAMIDE CONTAINING FREE GROUPS SELECTED FROM THE CLASS CONSISTING OF AMINE GROUPS AND CARBOXYL GROUPS, AND (C) A GLYCEROL-ADIPIC ACID POLYESTER HAVING AN ACID NUMBER FROM 50 TO 180, THE TOTAL AMOUNT OF POLYEPOXIDE, POLYAMIDE, AND POLYESTER DEPOSITED ON THE TEXTILE BEING ABOUT FROM 0.5 TO 10% OF THE WEIGHT OF THE TEXTILE, THE AMOUNT OF POLYESTER BEING ABOUT FROM 0.5 TO 2 PARTS BY WEIGHT FOR EACH PART BY WEIGH OF POLYEPOXIDE, AND CURING THE IMPREGNATED TEXTILE BY HEATING IT AT AN ELEVATED TEMPERATURE TO CURE AND INSOLUBILIZE THE POLYEPOXIDE, POLYAMIDE AND POLYESTER ON THE TEXTILE FIBERS. 